US010501625B2

United States Patent ( 10 ) Patent No.: US 10,501,625 B2

Marrou et al. (45 ) Date of Patent: Dec. 10 , 2019
(54 ) METHODS OF MAKING Johnson , Stephen et al. “ Effects of Divalent Cations, Seawater, and
ACRYLAMIDE - ACRYLIC ACID Formation Brine on Positively Charged Polyethylenimine/ Destran
COPOLYMERS Sulfate /Chromium (III )Polyelectrolyte Complexes and Partially Hydro
lyzed Polyacrylamide/Chromium ( III) Gelation.” Journal of Applied
(71) Applicant: Ecolab USA Inc. , St. Paul, MN (US ) Polymer Science, vol. 115 , 2010 , pp . 1008-1014 .
Sigale, Karine et al . “ Aspects of Crosslinking Sulfonated
(72 ) Inventors: Stephen Marrou , Mount Prospect, IL Polyacrylamides from Rheological Studies on Their Gels.” Journal
(US) ; Xiangyang Zhu , Denver, CO of Applied Polymer Science, vol. 64 , 1997 , pp . 1067-1072 .
(US ); Heqing Huang, Naperville , IL Bjørsvik ,Magny et al. “ Formation of colloidal dispersion gels from
(US) aqueous polyacrylamide solutions.” Colloids and Surfaces A :
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(73 ) Assignee : Ecolab USA Inc., St. Paul, MN (US) Muruaga , E. et al.“ Combining Bulk Gels and Colloidal Dispersion
Gels for Improved Volumetric Sweep Efficiency in a Mature
( * ) Notice: Subject to any disclaimer , the term of this Waterflood .” SPE International, 113334 , Apr. 2008 , 12 pages .
patent is extended or adjusted under 35 Wang , Wei et al. “ Applications of Weak Gel for In -Depth Profile
U.S.C. 154(b ) by 0 days . Modification and Oil Displacement.” Journal of Canadian Petro
( 21 ) Appl. No .: 15 / 190,364 leum Technology , vol. 42 , No. 6 , Jun. 2003. pp . 54-61.
Marudova - Zsivanovits, Mariya et al. “ Rheological Investigation of
Xanthan Gum - Chromium Gelation and Its Relation to Enhanced Oil
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160-166 .
(65 ) Prior Publication Data Smith , J.E. “ Performance of 18 Polymers in Aluminum Citrate
US 2016/0376390 A1 Dec. 29 , 2016 Colloidal Dispersion Gels.” SPE International, 28989 , Feb. 1995 ,
10 pages.
Related U.S. Application Data Zhidong, Guo et al. “ The Study ofOil Displacement Characteristics
(60 ) Provisional application No. 62 / 186,100 , filed on Jun . of CDG and Polymer Flooding." SPE International, 144119 , Jul.
29, 2015 . 2011, 14 pages .
Chang , Harry L. et al. “ Successful Field Pilot of In -Depth Colloidal
(51 ) Int. Cl. Dispersion Gel (CDG ) Technology in Daqing Oil Field .” SPE
C08F 222/38 (2006.01 ) International, 89460, Apr. 2004 , 15 pages .
C08L 71/02 (2006.01 ) Ranganathan , Raja et al. “ Experimental Study of the Gelation
CO8F 220/56 (2006.01 ) Behavior of a Polyacrylamide/Aluminum Citrate Colloidal
( 52 ) U.S. Cl. Dispersion Gel System .” SPE Journal, Dec. 1998, pp . 337-343.
CPC CO8L 71/02 (2013.01 ); C08F 220/56 Al-Assi, A.A. et al. “ Formation and Propagation ofGel Aggregates
( 2013.01) Using Partially Hydrolyzed Polyacrylamide and Aluminum Citrate.”
(58 ) Field of Classification Search SPE Journal, Sep. 2009, pp . 450-461.
CPC C08F 222/38 ; CO8L 71/02 Riahinezahad , Marzieh et al. “ Effect of Ionic Strength on the
See application file for complete search history . Reactivity Ratios of Acrylamide/ Acrylic Acid (sodium acrylate )
Copolymerization.” Journal of Applied Polymer Science , vol. 131,
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No. 20 , 2014 , 7 pages .
(56 ) Paril, Ahmet et al. “ Composition Control Through pH and Ionic
U.S. PATENT DOCUMENTS Strength During Acrylic Acid / Acrylamide Copolymerization .” Jour
nal of Applied Polymer Science , vol. 127 , No. 5 , 2012 , 7 pages.
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5,065,822 A 11/1991 Miller et al.
5,079,278 A 1/1992 Mitchell
5,480,933 A 1/1996 Fox et al.
6,387,986 B1 5/2002 Moradi- Araghi et al. Primary Examiner Robert D Harlan
6,723,781 B14/2004 Frat et al.
2006/0266488 A1 * 11/2006 Doherty D21H 21/10
(74 ) Attorney, Agent, or Firm — Kagan Binder, PLLC
162/ 164.1
2016/0032170 A1 * 2/2016 Li COOK 8/588
166 /305.1
(57 ) ABSTRACT
FOREIGN PATENT DOCUMENTS
A method ofmaking acrylamide- acrylic acid copolymers in
WO 2011/112470 A2 9/2011 water-in - oil latices is described . The method results in a
WO
WO
2011/113470
2011/113470 A1
9/2011
9/2011
copolymer having randomly distributed carboxylate func
tionalities and is suitable for ionic crosslinking. The copo
OTHER PUBLICATIONS lymers and their ionically crosslinked counterparts are use
ful for enhanced oil recovery processes .
Hassan , Saleh F. et al. “ Study of Polyacrylamide/ Cr (III ) Hydrogels
for Conformance Control in Injection Wells to Enhance Chemical
Flooding Process." SPE International, 168069 , May 2013, 11 pages. 19 Claims, No Drawings
 US 10,501,625 B2
Page 2
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OTHER PUBLICATIONS
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Acrylamide Acrylic Acid Copolymerization.” Journal of Applied
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Rintoul, Ignacio et al. “ Polymerization of ionic monomers in po
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Truong, N.D. et al. “Microstructure of acrylamide-acrylic acid
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Shawki, S.M. et al. “ Estimation of the Reactivity Ratios in the
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Squares Methods.” Journal of Applied Polymer Science , vol. 23 ,
No. 11, 1979 , pp . 3155-3166 .
Ponratnam , Surendra et al. “ Reactivity Ratios of Ionizing Mono
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1977, pp . 1029-1038 .
Rintoul et al., “ Polymerization of ionic monomers in polar solvents:
kinetics and mechanism of the free radical copolymerization of
acrylamide/acrylic acid ,” Polymer 46 , (2005) pp . 4525-4532 .
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US16 / 38903 , dated Sep. 6 , 2016 , 3 pages.
Written Opinion for International Application No. PCT/US16 /
38903, dated Sep. 6 , 2016 , 5 pages .
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US2016 /038905 , dated Sep. 11, 2016 , 3 pages .
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038905 , dated Sep. 11, 2016 , 5 pages .
Polymer Letters, “ Representation ofComposition and Blockiness of
the Copolymer by a Triangular Coordinate System ” , vol. 1, pp .
359-363 ( 1963) .
Halverson , et al., “ Sequence Distribution of Carboxyl Groups in
Hydrolyzed Polyacrylamide,” Macromolecules 18(6 ), pp . 1139
1144 ( 1985 ).
R.A.M. Thomson , “ A Kinetic Study of the Adiabatic Polymeriza
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Higuchi et al, Kinetic Aspects of the Alkaline Hydrolysis of
Poly( acrylamide), Polymer Journal, vol. 3, No. 3, pp . 370-377 ,
( 1972 ) .
European Search Report for European Application No. 16818492.7 ,
dated Jan. 8 , 2019 , pages.
* cited by examiner
 US 10,501,625 B2
1 2
METHODS OF MAKING showing the pH dependence of reactivity ratios r? (acrylam
ACRYLAMIDE - ACRYLIC ACID ide ) and r, (acrylic acid ) in copolymerization reactions
COPOLYMERS carried out at a total monomer concentration of 0.4 mol/L in
water at 40 ° C.
TECHNICAL FIELD 5
Reactivity ratios of AM (r,) and AA ( 12) at different pHs.
Reaction conditions: T =313 K , [AM ]+ [AA ] = 0.4 mol/ 1,
The invention relates to methods of making copolymers [K2S202] = 1.8x10-2 mol/1. Source : Rintoul and Wandrey,
of acrylamide and acrylic acid . Polymer 46 (2005), 4525-4532.
BACKGROUND 10
Reactivity ratios
Polyacrylamide (PAM ) and copolymers thereof with
acrylic acid (PAMAA ) are well known in the industry for a pH r1 r2
plethora of applications . Commercially important applica 1.8 0.54 1.48
tions of these copolymers include their use as flocculants in 15 2.7 0.69 1.34
water treatment or papermaking processes , as rheological 3.6
4.4
0.82
1.27
1.28
0.91
additives for water or waterbased solutions in applications 5.3 1.83 0.51
such as enhanced oil recovery (EOR ), or as water absorptive 6.2 2.50 0.39
agents when dried . 7.8 2.95 0.42
In dilute aqueous solutions, such as 1 wt % or less 20 8.8 3.05 0.42
commonly employed in EOR applications, PAM and its 12 3.04 0.32
copolymers are susceptible to chemical, thermal, and
mechanical degradation . The conditions encountered in Commercially , preparation of PAMAA is often carried out
EOR applications can include one or more of high shear, by partial hydrolysis of PAM homopolymer. This technique
harsh chemical environments, and temperatures of 70° C. 25 has the advantage of providing randomly distributed car
and higher. Chemical degradation occurs when the amide boxyl groups. Commercially , hydrolysis is carried out by
moiety hydrolyzes at elevated temperature and /or pH , result synthesizing or dispersing a PAM homopolymer in water,
ing in the evolution of ammonia and a residual carboxyl adding a concentrated sodium hydroxide solution , and heat
group. Thermal degradation of the vinyl backbone may ing the mixture. However, as noted above hydrolysis of
occur through any one or more of several possible radical 30 acrylamide functionality leads to evolution of ammonia
mechanisms. Mechanical degradation can also be an issue at (NH3), and so special equipment is required to carry out the
the high shear rates experienced in the near-wellbore region , procedure .
and within pumps and mixing devices designed to prepare Nonetheless, w /o latices are commercially significant
the EOR solutions for injection into a reservoir. sources of PAM and PAM copolymers for EOR applications
Cross -linked variants of polyacrylamide have shown 35 due to their high solids content (up to 60 wt % polymer)
greater resistance to all of thesemethods of degradation , and combined with low viscosity and rapid inversion to use
have proved to provide viscosity stability in EOR applica concentration , resulting in ease of use in the field .Due to the
tions. One commercially important type ofcrosslinked poly difficulty of post- emulsification , w /o laticesofPAM or PAM
mer used in EOR applications is PAMAA ionically cross copolymers are formed commercially by emulsifying the
linked via interaction of the acrylic acid moieties with 40 monomers and polymerizing in situ .
multivalent cations. Salts of Ca2+, Mg2+, Zn2+, Cr2+, Crd+, Thus, there is a need in the industry to provide w /o latices
and Al3+, for example, are employed commercially to form of PAMAA . There is a need in the industry to provide wlo
ionic crosslinks with the copolymers. In aqueous solutions, latices of PAMAA using methods that do not result in
such polymers have increased viscosity compared to evolution of NHz. There is a need in the industry to provide
uncrosslinked polymers. Additionally , the crosslinks are 45 ionically crosslinked PAMAA delivered from wlo latices.
capable of reforming after thermal ormechanical disruption There is a need in the industry to provide ionically cross
during use. In such ionically crosslinked systems, it is linked PAMAA delivered from w / o latices wherein the
desirable to employ a polymer having acrylic acid moieties amount of crosslinker required to reach a target viscosity
arranged randomly throughout the copolymer, because this upon inversion is about the same as the amount of cross
leads to maximum crosslink efficiency and the highest 50 linker required to reach the same viscosity for a PAMAA
possible effective molecular weight of the crosslinked com copolymer formed via hydrolysis of PAM . There is a need
position . As a practical matter, random acrylic acid place in the industry to provide w /o latices of PAMAA that are
ment in a copolymer leads to the observation that subsequent easily formed using conventional equipment.
ionic crosslinking is efficient in raising the viscosity of
aqueous solutions of the polymer; and a blockier copolymer 55 SUMMARY
requires more crosslinker to reach the same solution viscos
ity as a similar butmore random copolymer. Disclosed herein is a composition comprising a water-in
In theory there are two ways to form poly (acrylamide oil latex comprising a water phase and an oil phase , the
co -acrylic acid ): by directly copolymerizing acrylamide and water phase comprising water, acrylamide, and acrylic acid
acrylic acid, or by partially hydrolyzing an acrylamide 60 and having a pH of about 3 to 5 , or about 3.5 to 4 ; wherein
homopolymer. Direct copolymerization of acrylamide and the latex further comprises a surfactant mixture consisting
acrylic acid (or the conjugate base thereof) leads to compo essentially of nonionic surfactants and comprising a block
sitional drift of the produced copolymers due to the large copolymer. In some embodiments, the water phase consists
reactivity ratio differences. Rintoul and Wandrey, Polymer essentially of water, acrylamide, and acrylic acid , wherein
46 (2005), 4525-4532 have reported polymerization reac- 65 the pH of the water phase is about 3 to 5. In some
tivity ratios for acrylamide and acrylic acid as a function of embodiments, the ratio ofacrylamide to acrylic acid is about
several different variables. Reproduced below is a table 50:50 to 99 : 1, for example 60:40 to 98 :2 . In some embodi
 US 10,501,625 B2
3 4
ments, the block copolymer is a triblock copolymer com specification are not intended to be limiting and merely set
prising at least one block consisting essentially of ethylene forth some of the many possible embodiments for the
glycol repeat units and having an HLB of about 4 to 6. In appended claims.
some embodiments, the triblock copolymer further com
prises at least one block consisting essentially of hydroxy- 5 Definitions
acid repeat units . In some embodiments , the hydroxyacid is
12 -hydroxystearic acid . The term “ monomer" is used in context to mean either an
Also disclosed herein is a composition comprising a unsaturated compound or the polymerized residue thereof.
As used herein , “ acrylic acid ” means the unsaturated com
water - in -oil latex formed by a method comprising : combin 10 pound
ing water and monomers to form a water phase , the mono group having or the polymerized residue thereof bearing an acidic
mers comprising acrylamide and acrylic acid ; adjusting the thereof. a pKa of about 5 or less or the conjugate base
pH of the water phase to between about 3 and 5 ; combining As used herein , the term “ solution” means a compound
a hydrocarbon solventwith a surfactant mixture to form an dissolved or dispersed in a liquid . A polymer solution is a
oil phase , the surfactant mixture consisting essentially of 15 polymer substantially dispersed or dissolved in water or a
nonionic surfactants and comprising a block copolymer; waterbased solution . The polymer dispersion is a dispersion
contacting the water phase and the oil phase to form a as formed , or in the case of some EOR applications the
water- in -oil latex ; polymerizing the monomers to form a dispersion before injection , during injection , or after injec
copolymer, and neutralizing the water phase. In some tion as determined by context. Waterbased solutions include
embodiments, the composition further comprises the prod- 20 one or more dissolved salts , buffers, acids, bases, surfac
uct of diluting the composition with a water source after tants , or other dissolved , dispersed , or emulsified com
neutralizing, wherein the copolymer concentration after pounds, materials, components, or combinations thereof.
diluting is about 0.01 wt % to 1.00 wt % . In some embodi As used herein , the term “ latex ” refers to an emulsion or
ments, the water source comprises water and a salt of Ca2 +, sol in which each colloidal particle contains one or more
Mg2+, Cr2 +, Cr3+ ,Zn2 +, or A13 +, such as aluminum citrate or 25 polymers, or to an emulsion or sol in which each colloidal
chromium acetate . In some embodiments , the ratio of acry particle contains one or more monomers that are capable of
lamide to acrylic acid units in the copolymer is about 50:50 polymerization to form one or more polymers.
to 99: 1. In some embodiments, the neutralizing comprises comprising As used herein , the term " water" means a source of water
, consisting essentially of, or consisting of fresh
contacting the composition with a neutralizing solution , the 30 water, deionized
neutralizing solution comprising sodium hydroxide and an municipal water, waste water , distilled water , produced water ,
alkanolamide surfactant, such as N , N - diethanololeamide . water such as runoff water ormunici
pal waste water , well water
Also disclosed herein is a method ofmaking a water- in -oil sea water , or a combination , treated water, brackish water, or
copolymer latex , the method comprising : combining water sources as determined by context of two or more such water
and monomers to form a water phase, the monomers com 35 water source is at a temperature of . In some embodiments , the
prising acrylamide and acrylic acid ; adjusting the pH of the some embodiments, the water source about 20 ° C. to 90 ° C. In
water phase to between about 3 and 5 ; combining a hydro % total dissolved solids. The term “ waterbased has up to about 30 wt
” means a
carbon solvent with a surfactant mixture to form an oil composition including a water source listed herein .
phase , the surfactant mixture consisting essentially of non As used herein , the term “ stable” as applied to a water
ionic surfactants and comprising a block copolymer ; con- 40 in -oil latex means a kinetically stable latex that absent any
tacting the water phase and the oil phase to form a water force applied, temperature change , or chemical added to a
in -oil latex ; polymerizing the monomers to form a latex , the latex is or is capable of being substantially free of
copolymer; and neutralizing the water phase. In some coagulation , plating out, precipitation , gross coalescence of
embodiments, the latex is diluted with a water source after phases (conventionally referred to as " separation " ) or any
neutralizing to form a dilute solution , wherein the copoly- 45 other evidence of instability conventionally associated with
mer concentration after diluting is about 0.01 wt % to 1.00 water- in -oil latices for at least about 24 hours at about 20 °
wt % . In some embodiments, the water source comprises C. As used herein , the term " shelf stable ” means stable for
water and a salt of Ca2 +, Mg2+, Cr2+, Cr3+, Zn2+ , or Al3 +, at least six months at 20 ° C. or a selected temperature or
such as aluminum citrate or chromium acetate . In some range thereof.
embodiments, the neutralizing comprises contacting the 50 As used herein , the term “ optional” or“ optionally ” means
composition with a neutralizing solution , the neutralizing that the subsequently described event or circumstance may
solution comprising sodium hydroxide and an alkanolamide but need not occur, and that the description includes
surfactant such as N , N -diethanololeamide . instances where the event or circumstance occurs and
Additional advantages and novel features of the invention instances in which it does not.
will be set forth in part in the description that follows, and 55 As used herein , the term “ about” modifying , for example,
in part will become apparent to those skilled in the art upon the quantity of an ingredient in a composition , concentra
examination of the following, or may be learned through tion , volume, process temperature, process time, yield , flow
routine experimentation upon practice of the invention . rate , pressure, and like values , and ranges thereof, employed
in describing the embodiments of the disclosure , refers to
DETAILED DESCRIPTION 60 variation in the numerical quantity that can occur, for
example, through typical measuring and handling proce
Although the present disclosure provides references to dures used for making compounds, compositions, concen
preferred embodiments, persons skilled in the art will rec trates or use formulations; through inadvertent error in these
ognize that changes may be made in form and detail without procedures; through differences in the manufacture , source ,
departing from the scope of the invention . Reference to 65 or purity of starting materials or ingredients used to carry out
various embodiments does not limit the scope of the claims the methods, and like proximate considerations. The term
attached hereto . Additionally , any examples set forth in this “ about” also encompasses amounts that differ due to aging
 US 10,501,625 B2
5 6
of a formulation with a particular initial concentration or wt % to 90 wt % of the totalweight of the w /o latex , or about
mixture, and amounts that differ due to mixing or processing 45 wt % to 90 wt % , or about 50 wt % to 90 wt % , or about
a formulation with a particular initial concentration or 55 wt % to 90 wt % , or about 60 wt % to 90 wt % , or about
mixture . Where modified by the term “ about" the claims 40 wt % to 85 wt % , or about 40 wt % to 80 wt % , or about
appended hereto include equivalents according to this defi- 5 40 wt % to 75 wt % , or about 40 wt % to 70 wt % , or about
nition . Further, where “ about ” is employed to describe a 50 wt % to 80 wt % , or about 55 wt % to 75 wt % of the total
range of values, for example " about 1 to 5” the recitation weight of the w /o latex . In some embodiments, the monomer
means “ 1 to 5 ” and “ about 1 to about 5 " and “ 1 to about 5 " concentration in the water phase is about 50 wt % to 95 wt
and “ about 1 to 5 ” unless specifically limited by context. % of the total weight of the water phase , or about 55 wt %
As used herein , the term “ substantially ” means “ consist- 10 to 95 wt % , or about60 wt % to 95 wt % , or about 65 wt %
ing essentially of” , as that term is construed in U.S. patent to 95 wt % , or about 70 wt % to 95 wt % , or about 50 wt %
law , and includes “ consisting of ' as that term is construed in to 90 wt % , or about 50 wt % to 85 wt % or about 50 wt %
U.S. patent law . For example , a solution that is “ substan to 80 wt % , or about 50 wt % to 75 wt % , or about 60 wt %
tially free ” of a specified compound or materialmay be free to 90 wt % , or about 60 wt % to 85 wt % , or about 60 wt %
of that compound or material, or may have a minor amount 15 to 80 wt % of the total weight of the water phase of the wlo
of that compound or material present, such as through latex . In some embodiments, the molar ratio of AM :AA in
unintended contamination or incomplete purification. A the water phase is about 50:50 to 99 : 1, or about 55:45 to
“ minor amount” may be a trace , an unmeasurable amount, 99: 1, or about 60:40 to 99: 1 , or about 65:35 to 99: 1 , or about
an amount that does not interfere with or some other amount 70:30 to 99 : 1 , or about 50:50 to 98 :2 , or about 50:50 to 97 : 3 ,
as provided in context. A composition that has “ substantially 20 or about 50:50 to 96 :4 , or about 50:50 to 95 :5, or about
only ” a provided list of components may consist of only 50:50 to 90:10 , or about 50:50 to 85:15 , or about 50:50 to
those components , or have a trace amount of some other 80:20 , or about 60:40 to 70:30 , or about 60:40 to 95 :5 , or
component present, or have one or more additional compo about 60:40 to 97 :3 , or about 70:30 to 95 : 5 , or about 70:30
nents that do not materially affect the properties of the to 97 : 3 .
composition. Additionally, “ substantially ” modifying, for 25 In some embodiments , AM and AA make up substantially
example , the type or quantity of an ingredient in a compo the entire monomer complement in the w /o latex . In other
sition , a property , a measurable quantity, a method , a value, embodiments, up to 1 wt % of one or more additional
or a range, employed in describing the embodiments of the monomer(s ) are suitably included in the wlo latex , based on
disclosure , refers to a variation that does not affect the the total weight of monomer included in the latex . For
overall recited composition , property, quantity, method , 30 example about 0.001 wt % to 1.00 wt % , or about 0.01 wt
value , or range thereof in a manner that negates an intended
% to 1.00 wt % , or about 0.1 wt % to 1.00 wt % , or about
composition , property, quantity , method, value, or range.
0.2 wt % to 1.00 wt % , or about 0.3 wt % to 1.00 wt % , or
Where modified by the term “ substantially ” the claims
about 0.4 wt % to 1.00 wt % , or about 0.5 wt % to 1.00 wt
appended hereto include equivalents according to this defi
% , or about 0.6 wt % to 1.00 wt % , or about 0.7 wt % to 1.00
nition . 35 wt % , or about 0.8 wt % to 1.00 wt % , or about 0.1 wt % to
0.9 wt % , or about 0.1 wt % to 0.8 wt % , or about 0.1 wt %
DISCUSSION to 0.7 wt % , or about 0.1 wt % to 0.6 wt % , or about 0.1 wt
% to 0.5 wt % of one or more additional monomer (s) are
We have found that PAMAA polymers are suitably suitably included in the w /o latex , based on the total weight
formed by copolymerization of acrylamide (AM ) and acrylic 40 of monomer included in the latex . In some embodiments, a
acid (AA ) in w /o latices that are stable at pH of about 3.0 to useful additional monomer includes a long -chain hydrocar
5.0 . The latices are stable over this range of pH , and byl functionality intended to produce physicalor associative
acrylamide is stable to hydrolysis over this range as well. crosslinking in a waterbased polymer solution . Such hydro
The copolymers formed using this method are of similar phobically associating moieties are well known in the indus
molecular weight to PAM homopolymers polymerized in 45 try . In some embodiments, the hydrocarbyl functionality
w /o latices. The copolymers formed readily undergo ionic includes 8 to 20 carbons, or 10 to 20 carbons, or 12 to 20
crosslinking with salts of multivalent cations, wherein the carbons arranged in a linear , branched , or cyclic conforma
amount of crosslinker required to reach a target viscosity tion . In some embodiments, a useful additional monomer is
upon inversion (dilution and concomitant destabilization of 2 -acrylamido - 2-methylpropane sulfonic acid or the conju
the latex ) is about the same as the amount required to reach 50 gate base thereof. Other monomers are also usefully incor
the same viscosity for a PAMAA formed via hydrolysis of porated at amounts of up to 1 wt % of the total monomer
PAM . composition in the w /o latex.
Water- in - Oil Latex Polymerization The water phase of the wlo latex is formed by dissolving
Water -in -oil (w /o ) latices including monomers compris the monomers in water, then adjusting the pH of the water
ing, consisting essentially of, or consisting of acrylamide 55 phase prior to adding additional latex components. The pH
(AM ) and acrylic acid (AA ) are the starting point for of the water phase is advantageously adjusted to be about 2.0
polymerization to form PAMAA copolymers. The latices are to 5.0 , or about 2.2 to 5.0 , or about 2.4 to 5.0 , or about 2.6
stable during polymerization , subsequent neutralization, and to 5.0 , or about 2.8 to 5.0 , or about 3.0 to 5.0 , or about 3.2
storage of the neutralized latices. The copolymers thus to 5.0 , or about 3.4 to 5.0 , or about 3.6 to 5.0 , or about 3.8
formed have properties similar to or the same as hydrolyzed 60 to 5.0 , or about 2.0 to 4.8 , or about 2.0 to 4.6 , or about 2.0
PAM (HPAM ) of similar or the same molecular weight. to 4.4 , or about 2.0 to 4.2 , or about 2.0 to 4.0 , or about 3.0
To carry out copolymer synthesis, a copolymerization wlo to 4.5 , or about 3.5 to 4.5 , or about 3.7 to 4.3 , or about 3.7
latex is formed that comprises, consists essentially of, or to 4.0 . Compounds suitably added to the water phase to
consists of an oil phase and a water phase . reduce pH include protic acids capable of providing the
In some embodiments, the water phase comprises , con- 65 target pH and is unreactive otherwise in the wlo latex .
sists essentially of, or consists of a blend of AM and AA in Suitable protic acids include organic acids such as hydro
water. In various embodiments , the water phase is about 40 carbyl functional carboxylic and sulfonic acids, and inor
 US 10,501,625 B2
7 8
ganic acids. While many protic acids are useful in forming or more moieties derived from a sugar molecule are present
a low pH water phase , acids known to ionize 100 % in water in the nonionic surfactant. Examples of useful nonionic
are preferable from an efficiency standpoint, since less is surfactants include those having 4-10 ethoxylate groups
required to reach the target pH . Examples of suitable protic bonded to a sorbitolmoiety which in turn is bonded to a fatty
acids include hydrochloric acid , hydroiodic acid , hydrobro- 5 acid, such as ethoxylated sorbitan monooleate and ethoxy
mic acid , perchloric acid , nitric acid , and sulfuric acid . Other lated sorbitan monostearate . Other useful nonionic surfac
compounds suitably added to the water phase to increase pH tants include a linear, branched , cyclic , alicyclic , aromatic ,
to the target value include sodium hydroxide or other or alkaryl hydrocarbon group bonded to one or more moi
monovalent metalhydroxides. The compounds added to the eties derived from a sugar molecule ; examples include
water phase to reduce or increase pH are suitably added neat 10 sorbitan monostearate , sorbitan monooleate, and sorbitan
or in a waterbased solution , for example a 20 wt % to 50 wt monoisostearate .
% solution of the compound in a water source . In some embodiments, the surfactant or surfactant blend
One or more additional agents are suitably added to the comprises , consists essentially of, or consists of a polymeric
water phase , during or after formation thereof. Buffers, salts, nonionic surfactant. In some such embodiments , the poly
chain transfer agents, and chelators are examples of addi- 15 meric nonionic surfactant comprises , consists essentially of,
tional agents suitably added to the water phase . Such agents or consists of a poly ( ethylene glycol) ester of a fatty acid or
are added at suggested use levels or at levels determined by a long -chain hydrocarbon acid having about 10 to 30 , or
the targetwater source to be used to dilute the latices to their about 12 to 26 , or about 12 to 20 , or about 14 to 20 , or about
final concentration in the field . Suitable chain transfer agents 16 to 20 carbons. In some embodiments , the polymeric
include but are not limited to water soluble compounds such 20 nonionic surfactant is branched . In some embodiments the
as sodium hypophosphite . Suitable chelators include but are polymeric nonionic surfactant is hyperbranched . In some
not limited to tetrasodium ethylenediaminetetraacetic acid embodiments, the branched or hyperbranched polymeric
(EDTA ) . nonionic surfactant comprises, consists essentially of, or
The oil phase of the wlo latex is formed separately for consists of one or more poly (ethylene glycol) branches and
addition to the water phase. The oil phase includes a 25 one ormore fatty acid or long -chain hydrocarbon branches .
hydrocarbon solvent and one or more surfactants . In In some embodiments , the polymeric nonionic surfactant
embodiments, the hydrocarbon surfactant is present in the is a block copolymer. Block copolymers include those
oil phase at about 60 wt % to 99 wt % of the total weight of having one or more hydrophilic or water-soluble blocks and
the oil phase , or about 65 wt % to 99 wt % , or about 70 wt one or more hydrophobic or oil-soluble blocks, with the
% to 99 wt % , or about 75 wt % to 99 wt % , or about 80 wt 30 proviso that there is at least two hydrophilic blocks or two
% to 99 wt % , or about 85 wt % to 99 wt % , or about 90 wt hydrophobic blocks. In some embodiments, the block copo
% to 99 wt % , or about 95 wt % to 99 wt % , or about 97 wt lymer includes one or more ester linkages between one or
% 99 wt % , or about60 wt % to 98 wt % , or about 60 wt more blocks. Block copolymers wherein A is hydrophilic
% to 97 wt % , or about 60 wt % to 96 wt % , or about 60 wt block and B is a hydrophobic block are usefully employed
% to 95 wt % , or about 80 wt % to 98 wt % , or about 85 wt 35 where linear triblock ABA or BAB , tetrablock ABAB ,
% to 98 wt % , or about 90 wt % to 98 wt % , or about 90 wt pentablock ABABA or BABAB , or higher order structures
% to 97 wt % , or about 90 wt % to 96 wt % , or about 90 wt are employed . In some embodiments, the block copolymer
% to 95 wt % of the total weight of the oil phase . The is also branched or hyperbranched , with branches formed
hydrocarbon solvent is any compound or blend of com from one or more A blocks, B blocks, or both . In some
pounds that is liquid at 20 ° C.or lower includes substantially 40 embodiments, three or more different block structures ( thus,
only hydrogen and carbon . Generally , hydrocarbons having polymers including one or more A , B , and C blocks for
between 4 and 20 carbons are useful as the hydrocarbon example ) are employed in conjunction with the overall block
solvent or in a blend of compounds that together form the copolymer structures described above . In some embodi
hydrocarbon solvent for the oil phase. Aromatic , aliphatic , ments, one or more blocks are branched structures. In some
and aralkyl compounds such as linear , branched or cyclic 45 embodiments , one or more hydrophilic ( A ) blocks comprise ,
alkanes, alkenes , alkynes, aralkyl compounds, and the like consist essentially of, or consist of about 2 to 100 ethylene
are suitably employed in the oil phase. Paraffin oils or oxide repeat units, or about 4 to 50 , 2 to 50 , 2 to 40 , or 4 to
solvents , which are blends of petroleum distillates having a 40 ethylene oxide repeat units. In some embodiments , one or
stated boiling range, are examples of useful solvents for the more hydrophobic (B ) blocks comprise , consist essentially
oil phase. Suitable solvents include but are not limited to 50 of, or consist of repeat units derived from the condensation
dearomatized kerosene fractions such as KETRUL® D80 , of one or more hydroxyacids, wherein the hydroxyacids
sold by Total S.A. of Houston , Tex . In some embodiments, include a linear, branched , cyclic , or alicyclic hydrocarbon
the solvent is not flammable at temperatures of about 50 ° C. moiety having about 10 to 30 carbons. In some such
to 90 ° C. embodiments , the hydroxyacid is 12 -hydroxystearic acid
In some embodiments , the oil phase comprises, consists 55 (12 -hydroxyoctadecanoic acid ). In some embodiments , the
essentially of, or consists of the hydrocarbon solvent (s) and block copolymer has an HLB (hydrophilic - lipophilic bal
one or more surfactants . In embodiments , the surfactant ance) of about 4 to 6 , or about 4.5 to 6 , or about 4.5 to 5.5 ,
employed in the oil phase comprises, consists essentially of, or about 4.6 to 5.4 , or about 4.7 to 5.3 , or about 4.8 to 5.2 .
or consists of a surfactant blend of two or more surfactants, Useful block copolymer surfactants include those manu
or three or more surfactants. In embodiments , the surfactant 60 factured by Croda International PLC of Yorkshire , United
or surfactant blend comprises , consists essentially of, or Kingdom under the trade name HYPERMER® . One
consists of one or more nonionic surfactants. Examples of example of a useful surfactant is HYPERMER® 2524. In
useful nonionic surfactants include those having linear eth some embodiments, the surfactant is a blend of one ormore
ylene glycol, propylene glycol, or both glycol units in a short block copolymers and one or more conventional nonionic
(2-20 repeat units ) chain bonded to a linear, branched , 65 surfactant(s). Conventional nonionic surfactants include the
cyclic , alicyclic, aromatic , or alkaryl hydrocarbon group via non - polymeric surfactants listed above . In some such
an ether, ester, or amide linkage. In some embodiments, one embodiments, the weight ratio of the block copolymer
 US 10,501,625 B2
9 10
surfactant to conventional nonionic surfactant employed in Examples of suitable redox systems include t-butylhydrop
the oil phase is about 1:10 to 20 : 1, or about 1: 5 to 20 : 1, or eroxide/ ferrous ion ; ammonium persulfate/sodium bisulfite;
about 1: 2 to 20 : 1 , or about 1 : 1 to 20 : 1 , or about 1:10 to 18: 1 , and t-butylhydroperoxide/sodium metabisulfite. Typically ,
or about 1:10 to 16 : 1 , or about 1:10 to 14 : 1 , or about 1:10 the initiator(s) are dissolved in water and added to the wlo
to 12: 1, or about 1:10 to 10 :1 , or about 1:10 to 8 : 1, or about 5 latex at elevated temperature to initiate the polymerization
1:10 to 6 : 1, or about 1:10 to 4 : 1 , or about 1: 1 to 10 : 1, or The polymerization reaction is carried out in the latex for
about 1: 1 to 8 :1 , or about 1 : 1 to 6 :1 , or about 2 : 1 to 10 : 1 , or a sufficient amount of time to reach PAMAA weight-average
about 2 : 1 to 8 : 1, or about 2 : 1 to 6 : 1. In some embodiments , molecularweights ( M » ) of at least about 100,000 g/mol. The
the total amount of surfactant (including surfactant blends ) threshold molecular weight provides sufficient chain length
in the oil phase is about 0.1 wt % to 10 wt % based on the 10 to impart a desirable increase in viscosity when the polymer
total weight of the oil phase , or about 0.5 wt % to 10.0 wt is diluted for use in one or more EOR applications. In
% , or about 1.0 wt % to 10.0 wt % , or about 2.0 wt % to 10.0 embodiments, the Mw of the polymer compositions is about
wt % , or about 3.0 wt % to 10.0 wt % , or about 4.0 wt % to 100,000 to 10,000,000 g/mol, or about 500,000 to 8,000,000
10.0 wt % , or about 5.0 % wt % to 10.0 wt % , or about 6.0 g/mol, or about 500,000 to 5,000,000 g/mol, or about
wt % to 10.0 wt % , or about 7.0 wt % to 10.0 wt % , or about 15 1,000,000 to 5,000,000 g/mol. After polymerization is com
0.1 wt % to 9.9 wt % , or about 0.1 wt % to 9.7 wt % , or about plete , the w /o latex remains stable .
0.1 wt % to 9.5 wt % , or about 0.1 wt % to 9.0 wt % , or about After the polymerization is complete , the PAMAA copo
0.1 wt % to 8.5 wt % , or about 0.1 wt % to 8.0 wt % or about lymers in the w /o latices include about 50 mol % to 99 mol
5.0 wt % to 9.5 wt % , or about 7.0 wt % to 9.5 wt % , or about % AM , or about 55 mol % to 99 mol % AM , or about 60 mol
7.0 wt % to 9.0 wt % of the total weight of the oil phase. 20 % to 99 mol % AM , or about 65 mol % to 99 mol % AM ,
The surfactant or surfactant blend is added to the hydro or about 70 mol % to 99 mol % AM , or about 50 mol % to
carbon solvent with agitation , either neat or in a concen 95 mol % AM , or about 50 mol % to 90 mol % AM , or about
trated solution in the hydrocarbon solvent to be employed in 50 mol % to 85 mol % AM , or about 50 mol % to 80 mol
the w /o latex . In some embodiments , the combination of % AM , or about 50 mol % to 75 mol % AM , or about 50 mol
hydrocarbon solvent and surfactant or surfactant blend is 25 % to 70 mol % AM , or about 55 mol % to 80 mol % AM ,
heated to dissolve the surfactant. In some such embodi or about 60 mol % to 75 mol % AM , or about 65 mol % to
ments, the combination is heated to about 30 ° C. to 60 ° C. 75 mol % AM . In some embodiments, the remaining com
until the surfactant(s) dissolve. A surfactant blend is added ponent comprises, consists essentially of, or consists of
by sequentially adding each surfactant to the hydrocarbon acrylic acid . In other embodiments, up to 1 wt % of the total
solvent or as a formed mixture, depending on convenience 30 monomer mix , or the total copolymer composition, includes
of the user and equipment employed to mix the components. a third monomer.
After the water phase and the oil phase are independently Post - Treatment of the Water -in -Oil Latices
formed , the liquid phases are blended together to form After completion of polymerization the stable w /o latex is
a stable w /o latex . In some embodiments, blending is neutralized to a pH of about 5 to 7 , such as about 6 to 7, by
accomplished by adding the oil phase to the water phase , 35 adding a base such as sodium hydroxide to the latex to result
typically slowly or in aliquots and with efficient mixing in a stable neutralized w /o latex. In some embodiments, the
using conventional equipment to result in a stable latex . In base is dissolved in water prior to addition . In some embodi
embodiments , the weight ratio of the water phase :oil phase ments , a stabilizing surfactant is added to the base in water
in the latex after mixing is complete is about 5 : 1 to 1: 1, or to form a neutralization solution ; the neutralization solution
about 4.5 : 1 to 1: 1 , or about 4.0 : 1 to 1: 1 , or about 3.5 : 1 to 1: 1 , 40 is added to the wlo latex to form a stable neutralized wlo
or about 3.0 : 1 to 1 : 1 , or about 2.5 : 1 to 1 : 1 , or about 2 :1 to latex . The neutralization solution is added dropwise, batch
1 : 1, or about 5 : 1 to 1.5 : 1 , or about 5 : 1 to 2.0 : 1 , or about 5 : 1 wise or in a single addition to the w /o latex to form a
to 2.5 : 1, or about 5 : 1 to 3 : 1, or about 4 : 1 to 1.5 : 1, or about neutralized latex. In some embodiments , a solution of about
3 : 1 to 1.5 : 1 , or about 2.5 : 1 to 1 :5 : 1 . 25 wt % to 50 wt % sodium hydroxide or othermonovalent
After the stable w /o latex is formed , polymerization is 45 metal hydroxide is formed , and a stabilizing surfactant is
initiated . One of skill will recognize that the polymerization added to the solution at about 5 wt % to 10 wt % of the total
step is generally carried out according to conventional weight of the neutralization solution . In other embodiments ,
water- in -oil polymerization procedures and using standard a stabilizing surfactant is added to the w /o latex, followed by
free-radical initiators such as any of those found in the art addition of the base in water to form a neutralized w /o latex .
that are at least partially soluble in the water phase . While 50 The stabilizing surfactant comprises, consists essentially
not limited thereto , free radical and redox type chain reac of, or consists of a nonionic surfactant or blend of two or
tion methodologies are advantageously employed in some more nonionic surfactants having an HLB of about 2 to 15 ,
embodiments due to the known cost efficiency and ability to or about 3 to 15 , or about 4 to 15 , or about 5 to 15 , or about
form very high molecular weight species associated with 2 to 14 , or about 2 to 13 , or about 2 to 12 , or about 2 to 11 ,
such techniques. 55 or about 2 to 10 , or about 2 to 9 , or about 2 to 8 , or about
Thermally induced free radical polymerization is suitably 2 to 7 , or about 2 to 6 , or about 3 to 14 , or about 3 to 12 , or
initiated by adding a compound that decomposes homolyti about 3 to 10 , or about 3 to 8 , or about 3 to 6 , or about 4 to
cally at a known temperature to result in a free radical, which 14, or about 4 to 12 , or about 4 to 10 , or about 4 to 8 , or about
then proceeds to react with the unsaturated site of a mono 4 to 6. In some embodiments , the stabilizing surfactant
mer and initiate polymerization . Non -limiting examples of 60 includes amide , amine, triglyceride, or ether functionality . In
thermal free radical initiators include inorganic peroxides some embodiments , the stabilizing surfactant is a block
such as potassium persulfate. Redox polymerization is an copolymer including alkylene oxide functionality, such as
alternative technique employing a single electron transfer ethylene oxide or propylene oxide or both . In some embodi
reaction that has found wide application for initiating wlo ments, the surfactant includes one or more amine, amide,
latex polymerizations. Redox reactions are incurred by 65 ether, or triglyceride functionality . In some embodiments,
reduction of e.g. hydrogen peroxide or an alkyl hydrogen the stabilizing surfactant is an amide . In some such embodi
peroxide by Fe2+, Cr2 +, Cr3+, V2+, Ti3 +, Co2+, or Cu2+ salts . ments, the stabilizing surfactant comprises, consists essen
 US 10,501,625 B2
11 12
tially of, or consists of an N ,N -dialkanolamide, such as an linking a hydrolyzed PAM homopolymer of the same or
N ,N - diethanolamide ,having a hydrocarbon moiety of about similar molecular weight and molecular weight distribution .
12 to 30 carbons. Examples of useful N ,N - dialkanolamide Without being limited by theory, we believe that the ran
surfactants include those sold under the trade name AMI domized copolymerization enabled at the target pH results in
DEX® by the Lubrizol Corporation of Wickliffe , Ohio ; 5 a distribution of carboxylate moieties that is the same as or
examples include N , N -diethanololeamide (AMIDEX® O ) similar to the distribution of carboxylate moieties obtained
and N , N -diethanolcocamide (AMIDEX® CE ). by hydrolysis of a PAM homopolymer. This randomized
The neutralization solution is added to the wlo latex in an distribution , in turn , results in maximum crosslinking effi
amount that results in a pH of about 5 to 8 , or about 6 to 7 , ciency and thus maximum viscosification at the selected
further wherein the amount of the stabilization surfactant 10 level of crosslinking .
added to the latex is about 1 wt % or less of the total weight In embodiments, the amount of ionic crosslinker is
of the neutralized latex , for example about 0.1 wt % to 1.0 selected to provide a target viscosity of the PAMAA copo
wt % , or about 0.2 wt % to 1.0 wt % , or about 0.3 wt % to lymer when diluted to a target polymer flooding concentra
1.0 wt % , or about 0.4 wt % to 1.0 wt % , or about 0.5 wt % tion . The target polymer flooding concentration is about 1 wt
to 1.0 wt % , or about 0.6 wt % to 1.0 wt % , or about 0.1 wt 15 % or less of PAMAA in water, for example about 0.01 wt %
% to 0.9 wt % , or about 0.1 wt % to 0.8 wt % , or about 0.1 to 1.00 wt % , or about 0.02 wt % to 1.00 wt % , or about 0.03
wt % to 0.7 wt % , or about 0.1 wt % to 0.6 wt % , or about wt % to 1.00 wt % , or about 0.04 wt % to 1.00 wt % , or about
0.2 wt % to 0.9 wt % , or about 0.4 wt % to 0.8 wt % or about 0.05 wt % to 1.00 wt % , or about 0.06 wt % to 1.00 wt % ,
0.4 wt % to 0.7 wt % , or about 0.5 wt % to 0.7 wt % of the or about 0.07 wt % to 1.00 wt % , or about 0.08 wt % to 1.00
total weight of the neutralized latex . 20 wt % , or about 0.09 wt % to 1.00 wt % , or about 0.10 wt %
Neutralization results in a stable neutralized w / o latex to 1.00 wt % , or about 0.01 wt % to 0.90 wt % , or about 0.01
having a PAMAA copolymer dispersed therein . The neu wt % to 0.80 wt % , or about 0.01 wt % to 0.70 wt % , or about
tralized polymer is crosslinkable using a multivalent metal 0.01 wt % to 0.60 wt % , or about 0.01 wt % to 0.50 wt % ,
cation as described above . We have found that the neutral or about 0.01 wt % to 0.40 wt % , or about 0.01 wt % to 0.30
ized latices include a complement of carboxylate groups 25 wt % , or about 0.01 wt % to 0.20 wt % , or about 0.01 wt %
corresponding to the amount of acrylic acid originally added to 0.10 wt % , or about 0.02 wt % to 0.50 wt % , or about 0.03
to the water phase prior to polymerization . That is , the wt % to 0.50 wt % , or about 0.02 wt % to 0.30 wt % PAMAA
conditions during the copolymerization and neutralization in water. The target viscosity is selected by determining the
are sufficiently mild such that no hydrolysis of acrylamide viscosity of the petroleum product in the reservoir, wherein
amide groups to carboxylate groups is observed . 30 the target viscosity that is the same or similar to the viscosity
The PAMAA copolymers formed readily undergo ionic of the petroleum product. Thus, the concentration , degree of
crosslinking with salts of multivalent cations, wherein the crosslinking, molecular weight of the PAMAA copolymer,
amount of crosslinker required reach a target viscosity and the like in turn dictate the ideal concentration of
upon inversion ( dilution and concomitant destabilization of PAMAA copolymer in the polymer flooding solution .
the latex ) is about the same as the amount required to reach 35 In some embodiments, the amount of ionic crosslinker is
the same viscosity for a PAMAA formed via hydrolysis of selected to be about 1 wt % to 10 wt % based on the weight
PAM . Thus, in embodiments, one ormore ionic crosslinking of the PAMAA copolymer. Thus, in various embodiments,
agents are added to the w /o latex or the neutralized wlo latex the polymer flooding solution includes about 500 ppm (0.05
to form a crosslinked PAMAA copolymer. In some embodi wt % ) PAMAA and about 5 to 50 ppm ionic crosslinker; or
ments, ionic crosslinking of the PAMAA copolymers is 40 about 1000 ppm (0.10 wt % ) PAMAA and about 10 to 100
carried out by contacting the neutralized w /o latex with an ppm ionic crosslinker. Upon contacting PAMAA with an
ionic crosslinking agent, which is a salt bearing a divalent or ionic crosslinker , full crosslinking and thus peak solution
multivalent cation . In some embodiments the salt is added viscosity of the polymer flooding solutions is reached in
directly to the neutralized latex while in other embodiments about 1 hour to 10 days ; the amount of time to reach peak
the salt is dissolved in waterbefore adding to the neutralized 45 viscosity will depend on the processing methodology, tem
latex . In some embodiments , the salt is added contempora perature , and polymer concentration during inversion and/or
neously with dilution and inversion of the neutralized latex crosslinking .
in the field as the polymer is prepared for injection into a The peak viscosity of the polymer flooding solution after
reservoir . In still other embodiments , the salt is added prior contacting with ionic crosslinker is at least about 2 times
to or contemporaneously with the base used to neutralize the 50 (twice or 2x ) the viscosity of the same polymer flooding
w / o latex . solution without addition of the ionic crosslinker, for
Suitable ionic crosslinking agents include salts ofmulti example about 2x to 500x , or about5x to 500x , or about 10x
valent cations including but not limited to Ca2+, Mg2+, Zn2+, to 500x , or about 2x to 400x , or about 2x to 300x, or about
Cr2 +, Cr3+, and A13 + . While the counterion employed in 2x to 200x , or about 2x to 100x , or about 2x to 50x, or about
conjunction with the multivalent cations is not particularly 55 10x to 300x , or about 10x to 100x, or about 10x to 50x the
limited , in some embodiments organic counterions are use viscosity of the same polymer flooding solution without
fully employed . Examples of suitable organic counterions addition of the crosslinker. One of skill will appreciate that
include acetate , lactate, oxalate , maleate , succinate, glut viscosity increase depends on the amount of polymer,
arate , and citrate . Examples of suitable inorganic counteri amount of acrylic acid in the copolymer, type and amount of
ons include phosphonate, sulfonate , carbonate , halide such 60 crosslinker employed , and other factors such as temperature
as chloride or bromide, and the like . Thus, for example , a and type and amount of solids dissolved in the water source
solution of calcium oxalate , zinc chloride, magnesium used to form the polymer flooding solution .
acetate , or aluminum citrate in water is contacted with a Inversion of the Water -in -Oil Latices
neutralized w /o latex , before or during inversion, to result in The neutralized w /o latices are advantageously used in
a crosslinked PAMAA copolymer. It is a feature of the 65 one or more polymer flooding (EOR ) applications, where
invention that crosslinking results in a polymer solution they are inverted to provide a polymer flooding solution
viscosity commensurate with the results obtained by cross having about 1 wt % polymer or less . In some embodiments,
 US 10,501,625 B2
13 14
inversion is accomplished by adding a water source to the EXPERIMENTAL
neutralized latex so as to decrease the polymer concentration
and incur hydration of the polymer chains . In other embodi Example 1
ments, an inverting surfactant is further added to the latices
to stabilize the latex components during the inversion in 5
order to avoid coagulation or precipitation of the polymer. A water -in - oil latex was formed using the components
Dilution eventually destabilizes the latex structure , giving shown in Table 1 .
rise to disruption of the latex ; this is the process commonly
referred to as inversion . One of skill will appreciate that the TABLE 1
10
neutralized wlo latices formed using the methods of the Components of a w /o latex polymerization of AM and AA .
invention can be inverted employing standard inversion
materials and techniques: no special steps or devices are Composition Material Wt %
required .
Inversion of the neutralized w / o latex results in a polymer Oil Phase KETRUL ® D80 ( TOTAL Special 25.72
15 Fluids of Casablanca , Morocco )
flooding composition . In some embodiments , the polymer Sorbitan monooleate 0.31
flooding composition is formed in the field , wherein the POE (4 ) Sorbitan monostearate
( Polysorbate 61 )
1.24
neutralized w /o latex is delivered as the starting material for Tween 61 0.67
an EOR process and one or more water sources are present 20
Water Acrylamide (50.24 % in water ) 38.95
to accomplish the inversion . In some embodiments , one or Phase Acrylic Acid 8.23
more additional surfactants or inversion aids such as glyc DI Water 12.43
erol are added to the water source to facilitate the transition Sodium chloride 2.07
Sodium hypophosphite 0.002
of the latex to a dilute polymer solution . In some embodi Sodium hydroxide 0.835
ments, an ionic crosslinker as described above is added to 25 EDTA 0.0092
the water source used to invert the neutralized w / o latex . In Initiators Sodium metabisulfite 0.018
t-Butyl hydroperoxide 0.13
such embodiments , the ionic crosslinking compounds and Post N , N - diethanololeamide 0.62
methods described above are similarly applied except that Polymerization Sodium hydroxide 8.27
the crosslinking compounds are first dissolved in the water 30 Additives Ammonium thiocyanate 0.52
source to be used for inversion . In such embodiments,
inversion of the neutralized w /o latices contemporaneously A latex was formed by mixing the components of the
results in inversion and ionic crosslinking of the PAMAA water phase and oil phase separately, then combining them
copolymer in a reaction vessel with vigorous stirring using an overhead
In some embodiments , the polymer flooding composition 35 paddle
comprises, consists essentially of, or consists of a combi nitrogenblade . The
mixer followed by sparging of the latex with
pH of the water phase wasmeasured to be 3.7.
nation of the inverted , neutralized , ionically crosslinked After mixing was complete , the initiator composition was
PAMAA copolymer with a water source and optionally one added to the vessel and the vessel was sealed . The contents
or more inverting surfactants . In some embodiments , the 40 of the vessel were heated to 40 ° C.with stirring for about 4
polymer flooding composition is a combination of the hours. Then the post-treatment composition was mixed and
inverted , neutralized wlo latex with a water source and added to the vessel. Then the neutralization composition was
optionally one or more inverting surfactants. In some mixed and added to the vessel. The resulting neutralized wlo
embodiments, the water source comprises, consists essen latex was stable after cooling to ambient laboratory tem
tially of, or consists of fresh water, deionized water, distilled 45 perature and showed no sign of destabilization (separation ,
water, produced water ,municipalwater , waste water such as coagulum formation ) during the procedure . The reduced
runoff water or municipal waste water, well water, treated specific viscosity (RSV ) of the latex is 36 dL /g , as measured
water, brackish water, or sea water, or a combination of two at 450 ppm polymer concentration in 1M sodium nitrate
or more such water sources. In some embodiments, the solution using an Ubbelohde semimicro dilution viscometer,
water source is contacted with the neutralized w / o latex at a 50 size 75, held at 30 ° C. The latex was observed to be shelf
temperature of about 20 ° C.to 90 ° C., or about 50 ° C. to 90 ° stable in ambient laboratory conditions .
C. to accomplish the inversion. An aliquot of the latex was removed from the vessel after
It is a feature of the invention that the ionically cross the neutralization and was subjected to 13C NMR . The ratio
linked w /o latices result in polymer flooding solutions 55 ofcarboxamide:carboxylate content of the composition was
having viscosities that are commensurate with those determined to be about 70:30 , which reflects the molar ratio
obtained by conventional base catalyzed hydrolysis of PAM of acrylamide:acrylic acid monomers added to the water
homopolymers followed by ionic crosslinking . That is , phase.
dissolving a similar molecular weight PAM homopolymer in
water, hydrolyzing it to a target mole % carboxylate content 60 Example 2
that is commensurate with the AA content of the PAMAA
polymer synthesized according to the methods of the inven A water -in -oil latex including the materials shown in
tion , and ionically crosslinking the polymer yields a solution Table 2 was formed using the same procedure as outlined
of the same, substantially the same, or similar viscosity of 65 above for Example 1, except that no neutralization was
the PAMAA copolymers synthesized and inverted using the conducted post -polymerization . Components of the latex are
methods described herein . shown in Table 2 .
 US 10,501,625 B2
15 16
TABLE 2 ing to about 70/30 wt/wt acrylamide/acrylic acid , delivered
Components of a w /o latex polymerization of AM and AA .
as 90 wt % dry powder (EOR360 , obtained from TIORCO?
of Denver, Colo .), was diluted to a target concentration of
Composition Material Wt % 600 , 1000 , or 1200 ppm polymer using a solution of either
Oil Phase KETRUL ® D80 ( TOTAL Special 25.72
5 aluminum citrate (in 1 wt % NaCl) or chromium acetate ( in
Fluids of Casablanca , Morocco ) 3 wt % NaCl) as indicated in Table 4. The dilute polymer
Sorbitan monooleate 0.31 solutions with crosslinkers were heated to 50 ° C. Viscosity
POE (4 ) Sorbitan monostearate
(polysorbate 61)
1.24 was measured at t0 (initial diluted viscosity ) and after 5
Tween 61 0.67 10
days of stirring at 50 ° C. using an Anton -Paar MCR302
Water Acrylamide (50.24 % in water) 38.95 rheometer using double - gap concentric cylinder geometry
Phase Acrylic Acid 8.23 held constant at 25 ° C. The viscosities reported were taken
DI Water 12.43 from an average of the viscosity data collected at 1 data
sodium chloride 2.07
sodium hypophosphite 0.002 point every 10 seconds for 5 minutes. Results are shown in
Sodium hydroxide 9.10 15 Table 4 .
Initiators
EDTA
Sodium metabisulfite
0.0092
0.018
Example 4B : A 70/30 w /w % acrylamide /acrylic acid
tert-butyl hydroperoxide 0.13 copolymer was prepared according to the procedure of
Post Ammonium thiocyanate 0.52 Example 2. The latex was diluted to a target concentration
Polymerization
Additive of600 , 1000, or 1200 ppm polymer using a solution of either
20 aluminum citrate (in 1 wt % NaCl) or chromium acetate (in
The resulting wlo latex was stable after cooling to ambi 3 wt % NaCl) as indicated in Table 4. The dilute polymer
ent laboratory temperature and showed no sign of destabi solutions with crosslinkers were heated to 50 ° C. Viscosity
lization (separation , coagulum formation ) during the proce was measured at t= 0 (initial diluted viscosity ) and after 5
dure . The reduced specific viscosity (RSV ) of the latex was 25 days of stirring at 50 ° C. using an Anton -Paar MCR302
29.8 dL /g ,asmeasured at 450 ppm polymer concentration in rheometer using double- gap concentric cylinder geometry
1M sodium nitrate solution using an Ubbelohde semimicro held constant at 25 C. The viscosities reported were taken
dilution viscometer, size 75, held at 30 ° C. from an average of the viscosity data collected at 101/s for
Example 3 30 5 minutes ( 1 data point every 10 sec ). Results are shown in
Table 4 .
The compositions of Example 1 and Example 2 were acrylic Example 4C : A commercially prepared acrylamide/
subjected to ionic crosslinking conditions. Referring to acid copolymer having a composition corresponding
Table 3 , the indicated polymer latex was contacted with a 1 to about 70/30 wt/wt acrylamide/acrylic acid was delivered
wt % NaCl solution having the indicated amount of alumi 35 as 90 wt % dry powder (EOR380, obtained from TIORCO?
num citrate dissolved therein , to result in a dilute polymer of Denver, Colo .) and diluted to a target concentration of
solution having a polymer concentration as indicated in 600 , 1000, or 1200 ppm polymer using a solution of either
Table 3. Initial viscosity of the dilute solution was measured aluminum citrate (in 1 wt % NaCl) or chromium acetate (in
with an Anton -Paar MCR302 rheometer using double-gap 40 3 wt % NaCl) as indicated in Table 4. The dilute polymer
concentric cylinder geometry held constant at 25 ° C. The solutions with crosslinkers were heated to 50 ° C. Viscosity
viscosities reported were taken from an average of the was measured at t= 0 ( initial diluted viscosity ) and after 5
viscosity data collected at 1 data point every 10 seconds, for days of stirring at 50 ° C. using an Anton - Paar MCR302
5 minutes. After the viscosity was characterized , the dilute
solution was held at 50 ° C. for five (5 ) days in a convection 45 rheometer using double -gap concentric cylinder geometry
oven before remeasuring viscosity. The results are shown in held constant at 25 C. The viscosities reported were taken
Table 3 . from an average of the viscosity data collected at 10 1/s for
5 minutes (1 data point every 10 sec ). Results are shown in
TABLE 3 Table 4 .
Viscosity after contacting Ex . 1 and Ex. 2 polymers 50 Example 4D : A 70/30 wt/wtacrylamide/acrylic acid copo
with aluminum citrate in 1 wt % NaCl. lymer was prepared according to the procedure of Example
Polymer Al citrate t = 0 t = 5 days/50 ° 1. The latex was diluted to a target concentration of 600 ,
Sample (ppm ) (ppm ) n , cP n , cP 1000 , or 1200 ppm polymer using a solution of either
Ex . 1 600 15 8.8 14.2 55 aluminum citrate (in 1 wt % NaCl) or chromium acetate (in
(Low pH 600 30 9.2 275 3 wt % NaCl) as indicated in Table 4. The dilute polymer
Synthesis ) 1000 25 20.8 221 solutions with crosslinkers were heated to 50 ° C. Viscosity
Ex . 2
1000
600
50
15
20.8
10
1014
9.5
was measured at t= 0 ( initial diluted viscosity ) and after 5
(Neutral pH 600 30 9.8 9.4 days of stirring at 50 ° C. using an Anton - Paar MCR302
Synthesis ) 1000 25 21.2 20.5 60 rheometer using double -gap concentric cylinder geometry
1000 50 21.5 21.0 held constant at 25 C. The viscosities reported were taken
from an average of the viscosity data collected at 10 l/s for
5 minutes (1 data point every 10 sec ). Results are shown in
Example 4 Table 4 .
65 Reduced specific viscosity (RSV) was also measured at to
Example 4A : A commercially prepared hydrolyzed poly for each of the polymers 4A -4D (uncrosslinked ). The results
acrylamide homopolymer having a composition correspond are shown in Table 4 .
 US 10,501,625 B2
17 18
TABLE 4 6. The composition of claim 1 wherein the pH is about 3.5
to 4.0 .
Viscosity at day O and day 5 for diluted solutions of the 7. A composition comprising a water - in -oil latex formed
indicated polymer in the presence of the
indicated crosslinker at the stated amount. by a method comprising
5
a . combining water and monomers to form a water phase ,
Al citrate in 1
wt % NaCl
Cr acetate in 3
wt % NaCl
the monomers consisting of acrylamide and acrylic
acid ;
Cross n ,t = 5 n m,t = 5 b . adjusting the pH of the water phase to between about
RSV Poly linker t = 0 days @ t = 0 days @ 3.0 to 4.5 ;
Ex . ( dL / mer (Al or Cr) days 50 ° C. days 50 ° C. 10
No. (ppm ) (ppm ) (CP ) ( CP ) (CP) (CP ) c. combining a hydrocarbon solvent with a surfactant
mixture to form an oil phase , the surfactant mixture
4A 45 600
600
15
30
12.3
13.2
17.4
177
7.8
5.5
20.7
248
consisting essentially of nonionic surfactants and com
1000 25 24.4 48.8 18.8 24.5 prising a block copolymer;
1000
1200
50
30
26.9
33.5
1144
213
19.3
22.7
67.4
1141
15 d . contacting the water phase and the oil phase to form a
1200 60 33.9 1470 22.7 1262
water- in -oil latex ;
4B 41 600 15 10.0 9.5 5.7 432 e. polymerizing the monomers to form a copolymer; and
600 30 9.8 9.4 5.8 287 f. neutralizing the water phase .
1000
1000
25
50
21.2
21.5
20.5
21.0
12.0
12.6
647
847
8. The composition of claim 7 further comprising the
1200 30 28.1 27.1 16.9 854 20 product ofdiluting the composition with a water source after
1200 60 28.6 27.7 17.2 380 neutralizing, wherein the copolymer concentration after
4C 37 600
600
15
30
8.0
8.2
7.8
7.8
5.6
5.7
263
367
diluting is about 0.01 wt % to 1.00 wt % .
1000 25 16.3 15.8 10.6 472 9. The composition of claim 8 wherein the water source
1000 50 16.7 16.1 11.0 791 comprises water and a salt of Ca2 +, Fe+2, Fe +3, Mg2 +, Cr2+,
1200 30 21.4 20.8 14.1 915 25 Cr3+, Zn2 +, or A13 +.
4D 37
1200
600
60
15
22.0
8.8
21.0
14.2
14.8
5.5
1047
324
10. The composition of claim 9 wherein the salt is
600 30 9.2 275 5.5 180 aluminum citrate or chromium acetate .
1000 25 20.8 221 10.9 809 11. The composition of claim 7 wherein the ratio of
1000 50 20.8 1014 11.5 431 acrylamide to acrylic acid units in the copolymer is about
1200 30 28.3 373 15.4 294 30 50:50 to 99 : 1 .
1200 60 28.6 1527 15.6 1137
12. The composition of claim 7 wherein the neutralizing
comprises contacting the composition with sodium hydrox
The invention illustratively disclosed herein can be suit ide and an alkanolamide surfactant.
ably practiced in the absence of any element which is not 13. The composition of claim 12 wherein the alkanol
specifically disclosed herein. Additionally each and every 35 amide surfactant is N , N - diethanololeamide.
embodiment of the invention , as described herein , is 14. A method ofmaking a water -in -oil copolymer latex ,
intended to be used either alone or in combination with any thea method
. combining
comprising
water and monomers to form a water phase,
other embodiment described herein as well as modifications, the monomers consisting of acrylamide and acrylic
equivalents , and alternatives thereof. In various embodi 40 acid ;
ments, the invention suitably comprises, consists essentially b . adjusting the pH of the water phase to between about
of, or consists of the elements described herein and claimed 3.0 to 4.5 ;
according to the claims. It will be recognized that various c . combining a hydrocarbon solvent with a surfactant
modifications and changes may be made without following mixture to form an oil phase , the surfactant mixture
the example embodiments and applications illustrated and 45 consisting essentially of nonionic surfactants and com
described herein , and without departing from the scope of prising a block copolymer;
the claims. d . contacting the water phase and the oil phase to form a
water - in - oil latex ;
The invention claimed is : e . polymerizing the monomers to form a copolymer ; and
1. A composition comprising a water- in -oil latex , the 50 f. neutralizing the water phase .
water-in -oil latex comprising a water phase and an oil phase , 15. The method of claim 14 further comprising diluting
the water phase comprising water and monomers , themono the latex with a water source after neutralizing , wherein the
mers consisting of acrylamide and acrylic acid , wherein the copolymer concentration after diluting is about 0.01 wt % to
pH of the water phase is about 3.0 to 4.5 ; wherein the latex 1.00 wt % .
further comprises a surfactant mixture consisting essentially 55 16. The method of claim 15 wherein the water source
of nonionic surfactants and comprising a block copolymer. comprises water and a salt of Ca2 +, Mg2 +, Cr2 +, Cr3+ , Zn2 + ,
2. The composition of claim 1 wherein the ratio of or A13+ .
acrylamide to acrylic acid is about 60:40 to 99 : 1 . 17. The method of claim 16 wherein the salt is aluminum
3. The composition of claim 1 wherein the block copo citrate or chromium acetate .
lymer is a triblock copolymer comprising at least one block 60 18. The method of claim 14 wherein the neutralizing
consisting essentially of ethylene glycol repeat units and comprises contacting the composition with a neutralizing
having an HLB of about 4 to 6 . solution , the neutralizing solution comprising sodium
4. The composition of claim 3 wherein the triblock hydroxide and an alkanolamide surfactant.
copolymer further comprises at least one block consisting 19. A method of diluting a water-in -oil copolymer latex ,
essentially of hydroxyacid repeat units. 65 the method comprising adding a water source to the water
5. The composition of claim 4 wherein the hydroxyacid is in -oil copolymer latex of claim 14 after the neutralizing ,
12 -hydroxystearic acid . wherein the water source comprises water and a salt of Ca2 +,
 US 10,501,625 B2
19 20
Mg2 +, Cr2+ , Crd+, Zn2 +, or Al3 + ; and the copolymer con
centration after diluting is about 0.01 wt % to 1.00 wt % .